Triazine-ring-containing polymer and composition in which same is used

ABSTRACT

A triazine ring-containing polymer, having a structural unit represented by the following formula (1), in which a peak top molecular weight obtained by gel permeation chromatography is 19,000 or less.

TECHNICAL FIELD

The invention relates to a triazine ring-containing polymer, and acomposition in which the same is used, a thin film, a film, atransparent plate, a lens, an electronic device, a light-emitting deviceand an optical device.

BACKGROUND ART

A transparent resin such as a (meth)acrylic resin including polymethylmethacrylate, a polycarbonate resin, a transparent epoxy resin and atransparent silicone resin has lighter weight and more excellentprocessability, as compared with glass, and therefore has come to bewidely used for a windshield resin for aircraft or the like, atransparent container, a transparent coating agent or the like. Further,in recent years, a resin product such as a transparent resin lens hascome to be frequently used also in the field of optical components suchas spectacles.

Further, also in the field of an electronic material, theabove-described transparent resin is come to be frequently used for anapplication of an antireflection coating agent for a liquid crystaldisplay, a transparent coating agent for a solar battery, and an opticalelectronic material for a light-emitting diode, a photoreceiver of a CCD(charge-coupled device) image sensor or a CMOS (complementary metaloxide semiconductor) image sensor, or the like.

The applications of such optical electronic materials require not onlytransparency, but also a high refractive index for improvement in lightextraction efficiency or improvement in light condensing properties inmany cases.

In the conventional transparent resins, while mechanical physicalproperties can be controlled to some extent by a technique such ascrosslinking, a special technology has been required for enhancingoptical characteristics, particularly a refractive index.

Patent Documents 1 and 2 propose techniques in which a large amount of aheavy atom such as bromine and sulfur is bonded with an organic resin toimprove a refractive index. Moreover, Patent Documents 3 and 4 proposetechniques in which inorganic oxide fine particles having a highrefractive index are dispersed into an organic resin to improve arefractive index. Further, a high refractive index material composed ofa polymerizable triazine-based resin composition is also known (PatentDocument 5). Patent Document 6 describes a linear triazine-ring polymeror a triazine-ring-containing hyperbranched polymer.

According to the techniques in Patent Documents 1 and 2, the obtainedorganic resin is generally unstable to heat or light, and therefore aproblem of easily causing deterioration such as discoloration duringlong-term use remains, and also when the resin is used for anapplication of an electronic material component, corrosion of anelectrode, or the like is concerned. Moreover, the techniques in PatentDocuments 3 and 4 also have a problem of long-term storage stability orthe like of the obtained resin in which the fine particles aredispersed, and require a large amount of a dispersion stabilizer forimproving dispersion stability in the resin of the inorganic oxide fineparticles, and therefore balancing between the refractive index and thedispersion stability becomes difficult.

Moreover, according to the technique in Patent Document 5, while a highheat-resistant resin with a comparatively high refractive index isobtained, resulting from a triazine ring in a resin structure, therefractive index is not sufficiently high, and further an unsaturatedbonding site contributing to curing does not partially react andremains, and therefore such a problem as easily causing deteriorationsuch as discoloration and deformation during long-term use, or the likehas remained. According to Patent Document 6, the refractive index isfar from sufficiently high, and such a problem has occurred that,because of a hyperbranched polymer, physical properties of the polymerto be obtained are not stabilized depending on polymerization conditionssuch as temperature and an agitation state, and the polymer is formedinto insoluble gel depending on conditions.

Accordingly, a high refractive index material using a polymer containinga triazine ring is proposed (for example, Patent Documents 7 and 8).

CITATION LIST Patent Document

Patent Document 1: JP-A-H5-164901

Patent Document 2: JP-A-2005-350531

Patent Document 3: JP-A-2007-270099

Patent Document 4: JP-A-2007-308631

Patent Document 5: JP-A-2011-038015

Patent Document 6: WO2010/128661

Patent Document 7: JP-A-2014-162829

Patent Document 8: JP-A-2014-162830

SUMMARY OF INVENTION

An objective of the invention is to provide a triazine ring-containingpolymer excellent in solubility, and a composition in which the same isused, a thin film, a film, a transparent plate, a lens, an electronicdevice, a light-emitting device and an optical device.

The invention provides the following triazine ring-containing polymerand the like.

1. A triazine ring-containing polymer, comprising a structural unitrepresented by the following formula (1), wherein a peak top molecularweight obtained by gel permeation chromatography is 19,000 or less:

wherein, A represents a divalent group selected from the groupconsisting of —NH—, —NR″—, —NH—(C═O)—, —NR″—(C═O)—, —S— and —O—;

R′ represents a divalent aliphatic hydrocarbon group, a divalentaromatic hydrocarbon group, or a divalent group which is a combinationof (i) one or more selected from the group consisting of one or moredivalent aliphatic hydrocarbon groups and one or more divalent aromatichydrocarbon groups, and (ii) one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—; and R′ may be furthersubstituted with a substituent;

R represents a hydrogen atom, an aliphatic hydrocarbon group, anaromatic hydrocarbon group, an aliphatic hydrocarbon group having agroup which is a combination of an aromatic hydrocarbon group and one ormore selected from the group consisting of a single bond, —S—, —S(═O)₂—,—O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—, anaromatic hydrocarbon group having a group which is a combination of analiphatic hydrocarbon group and one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—, or an acetyl group; andR may be further substituted with a substituent;

R″ represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or a group which is a combination of one or more aliphatichydrocarbon groups and one or more aromatic hydrocarbon groups; and whena plurality of R″ exist, the plurality of R″ may be the same with ordifferent from each other.

2. The triazine ring-containing polymer according to 1, wherein an endgroup contains an amino group, —NHR¹ or —N(R¹)₂,

wherein R¹ independently represents —Si(R″)₃, —Si(OR″)₃, a group whichis a combination of —Si(OR″)₃ and a divalent group, R^(a)—(C═O)—, analiphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatichydrocarbon group having a group which is a combination of an aromatichydrocarbon group and one or more selected from the group consisting ofa single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—,—(C═O)—O—, —(C═O)—, a silylene group and a siloxylene group, or anaromatic hydrocarbon group having a group which is a combination of analiphatic hydrocarbon group and one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O—, —(C═O)—, a silylene group and asiloxylene group;

R¹ may be further substituted with a substituent;

R^(a) represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or an aliphatic hydrocarbon group having an aromatic hydrocarbongroup; and

R″ represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or a group which is a combination of one or more aliphatichydrocarbon groups and one or more aromatic hydrocarbon groups.

3. The triazine ring-containing polymer according to 1 or 2, wherein anextinction coefficient at a wavelength of 400 nm is 0.01 or less.

4. The triazine ring-containing polymer according to any one of 1 to 3,wherein R is an aliphatic hydrocarbon group which may have a substituentor an aromatic hydrocarbon group which may have a substituent, and R′ isa divalent group represented by any of the following formulas (5) to(11):

5. The triazine ring-containing polymer according to any one of 1 to 4,wherein R is a phenyl group, a p-cyanophenyl group or a p-nitrophenylgroup.

6. A composition, comprising the triazine ring-containing polymeraccording to any one of 1 to 5, and an organic solvent.

7. The composition according to 6, further comprising one or moreselected from the group consisting of an organic polymer, an inorganicpolymer and an organic-inorganic hybrid polymer.

8. The composition according to 6 or 7, further comprising anultraviolet curing agent or a thermosetting agent.

9. A thin film, a film, a transparent plate or a lens, prepared by usingthe triazine ring-containing polymer according to any one of 1 to 5 orthe composition according to any one of 6 to 8.

10. An electronic device, a light-emitting device or an optical device,comprising the thin film, the film, the transparent plate or the lensaccording to 9.

The invention can provide a triazine ring-containing polymer excellentin solubility, and a composition in which the same is used, a thin film,a film, a transparent plate, a lens, an electronic device, alight-emitting device and an optical device.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows an NMR chart of a compound A-1 obtained in SynthesisExample 1.

FIG. 2 shows an NMR chart of a triazine ring-containing polymer obtainedin Example 1.

DESCRIPTION OF EMBODIMENTS

A triazine ring-containing polymer of the invention has a structuralunit represented by the following formula (1), in which a peak topmolecular weight obtained by gel permeation chromatography is 19,000 orless.

Thus, solubility in a solvent can be improved, the polymer is dissolvedin various solvents, and a coating liquid (application liquid) forobtaining a thin film, a film, a transparent plate or a lens having ahigh refractive index can be prepared.

Further, a material giving a higher refractive index, as compared with aconventional high-refractive index material, can be obtained withoutusing a heavy atom involving a problem such as instability to heat orlight, and electrode corrosion, or a resin in which inorganic oxide fineparticles are dispersed, having a problem of long-term storage stabilityor a balance between a refractive index and dispersion stability.

Wherein, A represents a divalent group selected from the groupconsisting of —NH—, —NR″—, —NH—(C═O)—, —NR″—(C═O)—, —S— and —O—(preferably —NH—, —NH—(C═O)— or —S—);

R′ represents a divalent aliphatic hydrocarbon group, a divalentaromatic hydrocarbon group, or a divalent group which is a combinationof (i) one or more selected from the group consisting of one or moredivalent aliphatic hydrocarbon groups and one or more divalent aromatichydrocarbon groups, and (ii) one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—; and R′ may be furthersubstituted with a substituent;

R represents a hydrogen atom, an aliphatic hydrocarbon group, anaromatic hydrocarbon group, an aliphatic hydrocarbon group having agroup which is a combination of an aromatic hydrocarbon group and one ormore selected from the group consisting of a single bond, —S—, —S(═O)₂—,—O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—, anaromatic hydrocarbon group having a group which is a combination of analiphatic hydrocarbon group and one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—, or an acetyl group; andR may be further substituted with a substituent;

R″ represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or a group which is a combination of one or more aliphatichydrocarbon groups and one or more aromatic hydrocarbon groups; and whena plurality of R″ exist, the plurality of R″ may be the same with ordifferent from each other.

In the triazine ring-containing polymer of the invention, the peak topmolecular weight obtained by gel permeation chromatography (GPC) is19,000 or less, preferably 10,000 or less, and more preferably 8,000 orless, and from a viewpoint of solubility in isophorone or PGME(1-methoxy-2-propanol), further preferably 5,000 or less, andparticularly preferably 3,000 or less. A lower limit is not particularlylimited, but is 500 or more or 1000 or more, for example.

When the peak top molecular weight is 19,000 or less, the solubility inthe solvent increases, and the application liquid having a suitableconcentration can be prepared.

The peak top molecular weight Mp of the triazine ring-containing polymerof the invention can be determined, for example, by obtaining anequivalent to standard polystyrene for a molecular weight indicated bythe peak top of a chromatography chart obtained by the gel permeationchromatography using a column for size exclusion chromatography.

In the triazine ring-containing polymer of the invention, the extinctioncoefficient k₄₀₀ at a wavelength of 400 nm is preferably 0.5 or less,more preferably 0.1 or less, further preferably 0.01 or less, andparticularly preferably 0.005. A lower limit is not particularlylimited, but is 0.001, for example.

The lower limit is 0.5 or less, whereby transparency in a visible lightwavelength region is high, and visually observed coloration can bereduced.

The extinction coefficient can be measured by preparing the thin filmand using a spectroscopic ellipsometer, for example.

In the triazine ring-containing polymer of the invention, a refractiveindex n_(D) of a D line (589.3 nm) is preferably 1.7 or more. An upperlimit is not particularly limited, but is 1.9999, for example. Thus, forexample, a transparent thin film having higher reflectance, a thinnermicrolens array, or the like can be realized.

The Abbe number is preferably 5 or more. An upper limit is notparticularly limited, but is 15, for example. Thus, for example, anoptical thin film having small chromatic aberration can be realized.

The Abbe number means a numerical value representing wavelengthdispersion of the refractive index, and can be calculated by using therefractive indices of a D line (589.3 nm), an F line (486.1 nm), and a Cline (656.3 nm).

The refractive indices (n_(D), n_(F), and n_(C)) and the Abbe number canbe measured by using the spectroscopic ellipsometer, for example.

In the formula (1), the number of carbon atoms of the divalent aliphatichydrocarbon group of R′ is preferably 1 to 20. The number of ring carbonatoms of the divalent aromatic hydrocarbon group is preferably 6 to 20,and more preferably 6 to 10.

In R′, the divalent group which is the combination of (i) one or more(preferably two or more, more preferably two to three, and furtherpreferably two) selected from the group consisting of one or more(preferably two or more, more preferably two to three, and furtherpreferably two) divalent aliphatic hydrocarbon groups and one or more(preferably two or more, more preferably two to three, and furtherpreferably two) divalent aromatic hydrocarbon groups, and (ii) one ormore selected from the group consisting of the single bond, —S—,—S(═O)₂—, —O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O− and—(C═O)— is preferably a combination of two divalent aromatic hydrocarbongroups and one selected from the group consisting of —S—, —O—, —NH—,—NR″—, —(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—.

When a plurality of divalent aromatic hydrocarbon groups of R′ exist,the plurality of divalent aromatic hydrocarbon groups may be the samewith or different from each other.

When a plurality of divalent aliphatic hydrocarbon groups of R′ exist,the plurality of divalent aliphatic hydrocarbon groups may be the samewith or different from each other.

R′ is preferably a divalent aromatic hydrocarbon group, or a divalentgroup which is a combination of one or more divalent aromatichydrocarbon groups and one or more selected from the group consisting of—S—, —O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—,and more preferably a divalent aromatic hydrocarbon group.

R′ is preferably a divalent group represented by any of the followingformulas (5) to (11) from a viewpoint of the refractive index.

R′ may be further substituted with a substituent and the substituentswill be described later.

The number of carbon atoms of the aliphatic hydrocarbon group of R ispreferably 1 to 20. The number of ring carbon atoms of the aromatichydrocarbon group is preferably 6 to 20, and more preferably 6 to 10.

R is preferably an aromatic hydrocarbon group having 6 to 10 ring carbonatoms or an aromatic hydrocarbon group having a substituent and 6 to 10ring carbon atoms, and more preferably an aromatic hydrocarbon grouphaving a substituent and 6 to 10 ring carbon atoms.

R may be further substituted with a substituent and the substituentswill be described later.

R is preferably an aliphatic hydrocarbon group which may have asubstituent or an aromatic hydrocarbon group which may have asubstituent, from a viewpoint of the refractive index.

R is preferably a phenyl group, a p-cyanophenyl group or a p-nitrophenylgroup. Thus, the refractive index can be further enhanced.

The number of carbon atoms of the aliphatic hydrocarbon group of R″ ispreferably 1 to 20. The number of ring carbon atoms of the aromatichydrocarbon group is preferably 6 to 20, and more preferably 6 to 10.

R is preferably an aliphatic hydrocarbon group which may have asubstituent, or an aromatic hydrocarbon group which may have asubstituent, and R′ is preferably a divalent group represented by any ofthe formulas (5) to (11). Thus, the refractive index can be furtherenhanced.

Specific examples of the above-described substituent include an alkylgroup having 1 to 20 carbon atoms, a monocyclic or polycyclic cycloalkylgroup having 3 to 20 carbon atoms, an aralkyl group having 7 to 20carbon atoms, an aromatic hydrocarbon group (having preferably 6 to 20ring carbon atoms, and more preferably 6 to 10 ring carbon atoms), aheterocyclic group (having preferably 3 to 20 ring atoms, and morepreferably 3 to 10 ring atoms), and a heteroatom-containing substituent.

Specific examples of the above-described aliphatic hydrocarbon groupinclude an alkyl group having 1 to 20 carbon atoms, and a monocyclic orpolycyclic cycloalkyl group having 3 to 20 carbon atoms, and specificexamples of the alkyl group include a methyl group, an ethyl group, apropyl group, an isopropyl group, a n-butyl group, a s-butyl group, anisobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, an-heptyl group and a n-octyl group.

Specific examples of the cycloalkyl group include a group formed into analiphatic ring structure in the above-described example of the alkylgroup having 3 or more carbon atoms, and specific examples thereofinclude a cyclopentyl group and a cyclohexyl group.

Specific examples of the divalent aliphatic hydrocarbon group include agroup formed by eliminating one hydrogen atom from the above-describedgroup.

Specific examples of the above-described aromatic hydrocarbon group(aryl group) include a phenyl group, a 1-naphthyl group, a 2-naphthylgroup, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a4-phenanthryl group, a 9-phenanthryl group, a naphthacenyl group, achrysenyl group, a benzo[c]phenanthryl group, a benzo[g]chrysenyl group,a triphenylenyl group, a 1-fluorenyl group, a 2-fluorenyl group, a3-fluorenyl group, a 4-fluorenyl group, a 9-fluorenyl group, abenzofluorenyl group, a dibenzofluorenyl group, a 2-biphenylyl group, a3-biphenylyl group, a 4-biphenylyl group, a terphenyl group and afluoranthenyl group.

Specific examples of the divalent aromatic hydrocarbon group include agroup formed by eliminating one hydrogen atom from the above-describedgroup.

Specific examples of the aralkyl group include a group formed bysubstituting a hydrogen atom of the above-described alkyl group for theabove-described aryl group.

Specific examples of the heterocyclic group include a group formed of apyrrole ring, an isoindole ring, a benzofuran ring, an isobenzofuranring, a dibenzothiophene ring, an isoquinoline ring, a quinoxaline ring,a phenanthridine ring, a phenanthroline ring, a pyridine ring, apyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, anindole ring, a quinoline ring, an acridine ring, a pyrrolidine ring, adioxane ring, a piperidine ring, a morpholine ring, a piperazine ring, afuran ring, a thiophene ring, an oxazole ring, an oxadiazole ring, abenzoxazole ring, a thiazole ring, a thiadiazole ring, a benzothiazolering, a triazole ring, an imidazole ring, a benzimidazole ring, a pyranring, a dibenzofuran ring, a benzo[c]dibenzofuran ring, a carbazolering, and a derivative thereof.

Specific examples of the heteroatom-containing substituent include acyano group, an amino group, an alkylamino group, an arylamino group, anitro group, a thiol group, an alkylmercapto group, an arylmercaptogroup, an alkoxycarbonyl group or an alkoxycarbonyloxy group, acarbamoyl group and —NR²—C(═O)R³ (wherein, R² and R³ are independently ahydrogen atom or an aliphatic hydrocarbon group), and a cyano group, anitro group, an alkylmercapto group, an arylmercapto group, a carbamoylgroup or —NR²—C(═O)R³ is preferable.

Specific examples of the alkylamino group include a group formed bysubstituting one or two hydrogen atoms of the amino group for theabove-described alkyl group, and specific examples thereof include amethylamino group, a dimethylamino group, an ethylamino group, an-propylamino group, an isopropylamino group and a cyclohexylaminogroup.

Specific examples of the arylamino group include a group formed bysubstituting one or two hydrogen atoms of the amino group for theabove-described aryl group, and specific example thereof include ananilino group, a toluidino group, a mesidino group, or an anilino grouphaving a heteroatom-containing group such as a nitrogen atom-containinggroup, an oxygen atom-containing group and a sulfur atom-containinggroup.

Specific examples of the alkylmercapto group include a group formed bysubstituting a hydrogen atom of the mercapto group for theabove-described alkyl group, and specific example thereof include amethylthio group, an ethylthio group, a n-propylthio group and anisopropylthio group.

Specific examples of the arylmercapto group include a group formed bysubstituting a hydrogen atom of the mercapto group for theabove-described aryl group, and specific examples thereof include aphenylthio group and a naphthylthio group.

Specific examples of the alkoxycarbonyl group include a group formed bybonding the above-described alkyl group, an oxygen atom and a carbonylgroup in this order, and specific examples thereof include amethoxycarbonyl group and an ethoxycarbonyl group.

Specific examples of the alkoxy carbonyloxy group include a group formedby bonding the above-described alkyl group, a carbonyl group and anoxygen atom in this order, and specific examples thereof include amethoxycarbonyloxy group and an ethoxycarbonyloxy group.

Specific examples of the aliphatic hydrocarbon group of R² and R³include a group similar to the aliphatic hydrocarbon group of R.

In the triazine ring-containing polymer, the end group preferablycontains an amino group, —NHR¹ or —N(R¹)₂, and more preferably contains—NHR¹ or —N(R¹)₂ from viewpoints of improvement in solubility,suppression of deterioration during storage in association withremaining of an active end, and reduction of the coloration.

R¹ independently represents —Si(R″)₃, —Si(OR″)₃, a group which is acombination of —Si(OR″)₃ and a divalent group, R^(a)—(C═O)—, analiphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatichydrocarbon group having a group which is a combination of an aromatichydrocarbon group and one or more selected from the group consisting ofa single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—,—(C═O)—O—, —(C═O)—, a silylene group and a siloxylene group, or anaromatic hydrocarbon group having a group which is a combination of analiphatic hydrocarbon group and one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O—, —(C═O)—, a silylene group and asiloxylene group.

R¹ may be further substituted with a substituent.

R^(a) represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or an aliphatic hydrocarbon group having an aromatic hydrocarbongroup.

R″ represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or a group which is a combination of one or more aliphatichydrocarbon groups and one or more aromatic hydrocarbon groups.

The “divalent group” in the “group which is the combination of —Si(OR″)₃and the divalent group” is R′ in the formula (1), for example.

Specific examples of the aliphatic hydrocarbon group in R¹, R^(a) and R″include a group similar to the aliphatic hydrocarbon group of R in theformula (1).

Specific examples of the aromatic hydrocarbon group in R¹, R^(a) and R″include a group similar to the aromatic hydrocarbon group of R in theformula (1).

In R¹, specific examples of the substituent which may be furthersubstituted include a group similar to the substitute which may besubstituted, of R′ and R in the formula (1).

The end group is preferably isophorone, and from a viewpoint ofsolubility in PGME, a 4-isopropylphenylamino group, a phenylamino group,a n-butylamino group, a 3-(trimethoxysilyl)propylamino group, a3-[3′-(trimethoxysilyl)aminopropyl]aminopropylamino group and abis(trimethylsilyl)amino group, and particularly preferably an-butylamino group, a 3-(trimethoxysilyl)propylamino group, a3-[3′-(trimethoxysilyl)aminopropyl]aminopropylamino group and abis(trimethylsilyl)amino group.

The triazine ring-containing polymer of the invention can bemanufactured, for example, by allowing a polymerization reaction betweena dichloro monomer of a triazine ring having R-A- and a diamine monomerrepresented by NH₂—R′—NH₂ (R and R′ are as defined in the formula (1)).

As a polymerization solvent, super dehydrated N,N-dimethylacetamide,super dehydrated N,N-dimethylformamide, guaranteedN,N-dimethylacetamide, guaranteed N, N-dimethylformamide, superdehydrated N-methyl-2-pyrrolidone, guaranteed N-methyl-2-pyrrolidone,guaranteed 1,3-dimethyl-2-imidazolidinone or the like may be used. Fromviewpoints of the solubility of the dichloro monomer of the triazinering having R-A-, the solubility of the diamine monomer represented byNH₂—R′—NH₂, suppression of the coloration and reduction of theextinction coefficient, super dehydrated N,N-dimethylacetamide, superdehydrated N,N-dimethylformamide or super dehydratedN-methyl-2-pyrrolidone is preferable.

A polymerization atmosphere may be under a nitrogen atmosphere, underatmospheric air, under reduced pressure, in vacuum, under pressure ofnitrogen or the like. From viewpoints of simplicity of a manufacturingapparatus, suppression of the coloration and reduction of the extinctioncoefficient, a state under a nitrogen atmosphere is preferable.

A polymerization temperature is ordinarily 50° C. or higher, and fromviewpoints of suppression of the coloration and improvement in thesolubility, preferably 80° C. or higher, and more preferably 120° C. orhigher. An upper limit is not particularly limited, but is preferably200° C. or lower.

A polymerization time is ordinarily 1 to 24 hours.

After the polymerization reaction, an end-capping agent may be addedthereto and allowed to react with the polymer.

Specific examples of the end-capping agent include NH₂R¹, NH(R′)₂ andcarboxylic anhydride (R¹ is as defined in R¹ of the above-described endgroup).

Thus, the solubility can be improved, the deterioration during storagein association with remaining of the active end can be suppressed, andthe coloration can be reduced.

A reaction temperature of the end-capping agent is ordinarily 100 to200° C., and a reaction time is ordinarily 1 to 24 hours.

The peak top molecular weight of the triazine ring-containing polymer tobe obtained can be adjusted by taking into account the solubility of thediamine monomer to be used in the polymerization solvent, interaction ofthe polymerization solvent to be used to the polymerization reaction,the polymerization temperature, and the like.

Specific examples of the carboxylic anhydride include acetic anhydride,propionic anhydride, succinic anhydride and maleic anhydride.

From a viewpoint of suppressing the coloration, it is preferable to heatthe diamine monomer, and add the dichloro monomer thereto.

A composition of the invention contains the triazine ring-containingpolymer of the invention and the organic solvent.

A content of the triazine ring-containing polymer is selected in therange of 0.1 to 50% by mass based on the total composition, for example.

As the organic solvent, any solvent can be used in the range in whichthe above-described triazine ring-containing polymer is dissolvedtherein, and specific examples thereof include an amide-based solventsuch as N-methyl-2-pyrrolidone, N,N-dimethylformamide,N,N-dimethylacetamide and 1,3-dimethyl-2-imidazolidinone; ahalogen-based solvent such as 1,1,2,2-tetrachloroethane, chloroform anddichloromethane; a ketone-based solvent such as cyclohexanone and methylethyl ketone; an ester-based solvent such as ethyl acetate; anether-based solvent such as tetrahydrofuran; an glyme-based solvent suchas 1-methoxy-2-propanol and diethylene glycol monoethyl ether; andisophorone.

From a viewpoint of the solubility of the triazine ring-containingpolymer, an amide-based solvent is preferable. Moreover, from aviewpoint of toxicity, a glyme-based solvent or isophorone ispreferable.

A content of the organic solvent cannot be unconditionally defineddepending on a kind of the triazine ring-containing polymer to be used,a kind of the solvent, an application of the composition or useconditions or the like, but is ordinarily 50 to 99.9% by mass based onthe total composition.

The composition of the invention may contain a polymer other than thetriazine ring-containing polymer. Specific examples of the polymer otherthan the triazine ring-containing polymer include an organic polymer, aninorganic polymer and an organic-inorganic hybrid polymer.

Specific examples of the organic polymer include polyacrylate,polymethacrylate, polycarbonate, polyimide, polyamide and an epoxyresin.

Specific examples of the inorganic polymer include polysiloxane,polytitanoxane and polyzirconoxane.

Specific examples of the organic-inorganic hybrid polymer includepolyalkylsiloxane.

The polymers other than the triazine ring-containing polymer may be usedalone in one kind, or in combination of two or more kinds.

When the composition contains the polymer other than the triazinering-containing polymer, a content of the polymer other than thetriazine ring-containing polymer is preferably 0.1 to 99.9% by massbased on the total composition.

Moreover, the composition of the invention may contain an ultravioletcuring agent.

Specific examples of the ultraviolet curing agent include aconventionally-known agent, such as persulfate including ammoniumpersulfate; an azo compound including 4,4′-azobis(4-cyanovaleric acid);a diacyl peroxide compound including isobutyryl peroxide; and aperoxydicarbonate compound includingbis(4-t-butylcyclohexyl)peroxydicarbonate.

When the composition contains the ultraviolet curing agent, a content ofthe ultraviolet curing agent is preferably 0.001 to 10% by mass based onthe total composition.

The composition of the invention may contain a thermosetting agent.

Specific examples of the thermosetting agent include a publicly-knownagent, such as an aliphatic amine-based curing agent for an epoxy resinand a polyisocyanate-based curing agent.

When the composition contains the thermosetting agent, a content of thethermosetting agent is preferably 0.01 to 30% by mass based on the totalcomposition.

Moreover, as any other additive, a curing catalyst, a stabilizer, afilm-thickness adjusting material, a leveling material, a transparentimproving material, a strength improving material or the like may beadded thereto. A kind thereof, an amount of addition or the like may beappropriately adjusted according to the triazine ring-containing polymeror the like contained in the composition.

The composition of the invention consists essentially of the triazinering-containing polymer, and the organic solvent, and arbitrarily thepolymer other than the triazine ring-containing polymer, the ultravioletcuring agent and the thermosetting agent, and may contain inevitableimpurities in addition thereto within the range in which advantageouseffects of the invention are not adversely affected.

For example, 80% by mass or more, 90% by mass or more, 95% by mass ormore, 98% by mass or more or 100% by mass of the composition of theinvention may be composed of:

the triazine ring-containing polymer, and the organic solvent; or

the triazine ring-containing polymer, and the organic solvent, andarbitrarily the polymer other than the triazine ring-containing polymer,the ultraviolet curing agent and the thermosetting agent.

The thin film, the film, the transparent plate, the lens, or the likecan be prepared by using the triazine ring-containing polymer of theinvention or the composition of the invention.

The thin film, the film, the transparent plate and the lens of theinvention can be used for an electronic device, a light-emitting deviceor an optical device.

The thin film of the invention is preferably manufactured by applyingthe above-described composition onto a substrate.

The substrate is not particularly limited, and a publicly-knownsubstrate can be used. Specific examples thereof include a glasssubstrate, a synthetic quartz substrate, a silicon substrate and a resinfilm substrate such as a polyethylene terephthalate substrate, apolyethylene naphthalate substrate and a cycloolefin copolymersubstrate.

Moreover, an application method is not particularly limited, and apublicly-known method can be used. Specific examples thereof includespin coating, bar coating, flow coating, casting, dip coating and spraycoating.

Drying may be performed after coating.

A drying temperature is ordinarily 50 to 300° C. A drying time isordinarily 30 seconds to 1 hour.

EXAMPLES Synthesis Example 1

In a 500 mL three-necked flask equipped with a low-temperaturethermometer of −50° C. to 50° C., a 100 mL dropping funnel and a Dimrothcondenser, an acetone 200 mL solution of 18.44 g (100 mmol) of cyanuricchloride was put, and the resulting mixture was cooled to 0° C. in asalt/ice bath. While the cooled solution was stirred, an acetone 50 mLsolution of 11.81 g (100 mmol) of 4-cyanoaniline was added dropwisethereto for 20 minutes from the dropping funnel while confirming that atemperature of a reaction liquid was not more than 5° C., and aftercompletion of dropwise addition, the resulting mixture was stirred at 5°C. for 1 hour. Then, contents were charged into 500 mL of pure water,and a precipitated solid was filtered off. The resulting solid washedwith 500 mL of pure water until wash water became neutral was driedunder reduced pressure at 80° C. for 8 hours to obtain 25.97 g (97.60mmol, yield: 97.6%) of 2-(4-cyanoanilino)-4,6-dichlorotriazine (compound(compound A-1) represented by the following formula (A-1)). An NMR chartof the compound A-1 obtained is shown in FIG. 1.

Synthesis Example 2

A compound A-2 (compound represented by the following formula (A-2)) wasobtained in the same manner as in Synthesis Example 1 except that 13.81g (100 mmol) of 4-nitroaniline was used in place of 11.81 g (100 mmol)of 4-cyanoaniline.

Synthesis Example 3

A compound A-3 (compound represented by the following formula (A-3)) wasobtained in the same manner as in Synthesis Example 1 except that 9.31 g(100 mmol) of aniline was used in place of 11.81 g (100 mmol) of4-cyanoaniline.

Example 1

In a 100 mL three-necked flask equipped with a 200° C. thermometer and aDimroth condenser, 0.54 g (5 mmol) of p-phenylenediamine was put as adiamine monomer, and an atmosphere was replaced by nitrogen. In thisthree-necked flask, 5 mL of super dehydrated N,N-dimethylacetamide (madeby Wako Pure Chemical Industries, Ltd., hereinafter, referred to assuper dehydrated DMA) was put as a polymerization solvent under nitrogenflow, and the resulting mixture was stirred for 5 minutes in an oil bathpreviously set to 150° C. and was dissolved. Into this solution, asolution prepared by using 1.33 g (5 mmol) of2-(4-cyanoanilino)-4,6-dichlorotriazine (compound A-1) obtained inSynthesis Example 1 as a dichloro monomer and 7.5 mL of super dehydratedDMA under nitrogen flow was charged by using a syringe under nitrogenflow, and the resulting solution was stirred at a polymerizationtemperature of 150° C. for 4 hours under nitrogen flow, and thepolymerization was proceeded.

Then, 0.71 mL (5 mmol) of 4-isopropylaniline was charged thereinto as anend-capping agent by using a syringe under nitrogen flow, and theresulting solution was stirred at 150° C. for 2 hours to perform anend-capping reaction, and then the reaction solution was left to cool toroom temperature.

This solution was charged into 100 mL of 1.25% ammonia water, and aprecipitated solid was filtered off. This solid was washed with ionexchange water, and dried under reduced pressure at 120° C. for 2 hoursto obtain a white polymer (mixture of a polymer represented by thefollowing formula (B-1) and a polymer represented by the followingformula (B-1′) in which only an end group is different (wherein, eachformula indicates that a structural unit in brackets is repeated.)). AnNMR chart of the polymer obtained is shown in FIG. 2.

A peak top molecular weight Mp of the polymer obtained was determined bygel permeation chromatography (GPC) under the following measurementconditions. The results are shown in Table 1.

In addition, only the end group is different between the polymerrepresented by the formula (B-1) and the polymer represented by theformula (B-1′), and the peak top molecular weight is substantially thesame between both polymers.

Apparatus: Alliance e2695 (made by Waters Corporation)

Detector: differential refractometer

Column: Shodex KF-806M (made by Showa Denko K.K.), two columns

Column temperature: 60° C.

Solvent: N-methyl-2-pyrrolidone solution of LiBr (0.01 M)

Flow rate: 0.7 mL per minute

Sample concentration: 0.1 w/v % (solution prepared by dissolving 10 mgof a sample in 10 mL of the above-described solvent)

Sample injection volume: 100 μL

Standard sample: TSK standard polystyrene (made by Tosoh Corporation)

(Solubility in Isophorone 1)

The above-described polymer was mixed with isophorone to be 10% byweight. A dissolved state thereof was visually observed after mixing. Acase where the polymer was completely dissolved therein is taken asgood. A case where bulkiness of the polymer after mixing was visuallyreduced than bulkiness of the polymer before mixing, but the polymerremained without being dissolved, or a case where the solution wascolored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in Isophorone 2)

The above-described polymer was mixed with isophorone to be 20% byweight. A dissolved state thereof was visually observed after mixing. Acase where the polymer was completely dissolved therein is taken asgood. A case where bulkiness of the polymer after mixing was visuallyreduced than bulkiness of the polymer before mixing, but the polymerremained without being dissolved, or a case where the solution wascolored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in PGME 1)

The above-described polymer was mixed with PGME (1-methoxy-2-propanol)to be 10% by weight. A state of dissolution was visually observed aftermixing. A case where the polymer was completely dissolved therein istaken as good. A case where bulkiness of the polymer after mixing wasvisually reduced than bulkiness of the polymer before mixing, but thepolymer remained without being dissolved, or a case where the solutionwas colored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in PGME 2)

The above-described polymer was mixed with PGME to be 20% by weight. Astate of dissolution was visually observed after mixing. A case wherethe polymer was completely dissolved therein is taken as good. A casewhere bulkiness of the polymer after mixing was visually reduced thanbulkiness of the polymer before mixing, but the polymer remained withoutbeing dissolved, or a case where the solution was colored, or a casewhere the solution became cloudy is taken as marginal. A case where thepolymer was not dissolved therein is taken as poor. The results areshown in Table 1.

(Solubility in DMA 1)

The above-described polymer was mixed with DMA (N,N-dimethylacetamide)to be 10% by weight. A state of dissolution was visually observed aftermixing. A case where the polymer was completely dissolved therein istaken as good. A case where bulkiness of the polymer after mixing wasvisually reduced than bulkiness of the polymer before mixing, but thepolymer remained without being dissolved, or a case where the solutionwas colored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in DMA 2)

The above-described polymer was mixed with DMA to be 20% by weight. Astate of dissolution was visually observed after mixing. A case wherethe polymer was completely dissolved therein is taken as good. A casewhere bulkiness of the polymer after mixing was visually reduced thanbulkiness of the polymer before mixing, but the polymer remained withoutbeing dissolved, or a case where the solution was colored, or a casewhere the solution became cloudy is taken as marginal. A case where thepolymer was not dissolved therein is taken as poor. The results areshown in Table 1.

(Solubility in DMF 1)

The above-described polymer was mixed with DMF (N,N-dimethylformamide)to be 10% by weight. A state of dissolution was visually observed aftermixing. A case where the polymer was completely dissolved therein istaken as good. A case where bulkiness of the polymer after mixing wasvisually reduced than bulkiness of the polymer before mixing, but thepolymer remained without being dissolved, or a case where the solutionwas colored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in DMF 2)

The above-described polymer was mixed with DMF so as to be 20% byweight. A state of dissolution was visually observed after mixing. Acase where the polymer was completely dissolved therein is taken asgood. A case where bulkiness of the polymer after mixing was visuallyreduced than bulkiness of the polymer before, mixing, but the polymerremained without being dissolved, or a case where the solution wascolored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in NMP 1)

The above-described polymer was mixed with NMP (N-methyl-2-pyrrolidone)to be 10% by weight. A state of dissolution was visually observed aftermixing. A case where the polymer was completely dissolved therein istaken as good. A case where bulkiness of the polymer after mixing wasvisually reduced than bulkiness of the polymer before mixing, but thepolymer remained without being dissolved, or a case where the solutionwas colored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in NMP 2)

The above-described polymer was mixed with NMP so as to be 20% byweight. A state of dissolution was visually observed after mixing. Acase where the polymer was completely dissolved therein is taken asgood. A case where bulkiness of the polymer after mixing was visuallyreduced than bulkiness of the polymer before mixing, but the polymerremained without being dissolved, or a case where the solution wascolored, or a case where the solution became cloudy is taken asmarginal. A case where the polymer was not dissolved therein is taken aspoor. The results are shown in Table 1.

(Solubility in 1,3-dimethyl-2-imidazolidinone 1)

The above-described polymer was mixed with1,3-dimethyl-2-imidazolidinone to be 10% by weight. A state ofdissolution was visually observed after mixing. A case where the polymerwas completely dissolved therein is taken as good. A case wherebulkiness of the polymer after mixing was visually reduced thanbulkiness of the polymer before mixing, but the polymer remained withoutbeing dissolved, or a case where the solution was colored, or a casewhere the solution became cloudy is taken as marginal. A case where thepolymer was not dissolved therein is taken as poor. The results areshown in Table 1.

(Solubility in 1,3-dimethyl-2-imidazolidinone 2)

The above-described polymer was mixed with1,3-dimethyl-2-imidazolidinone to be 20% by weight. A state ofdissolution was visually observed after mixing. A case where the polymerwas completely dissolved therein is taken as good. A case wherebulkiness of the polymer after mixing was visually reduced thanbulkiness of the polymer before mixing, but the polymer remained withoutbeing dissolved, or a case where the solution was colored, or a casewhere the solution became cloudy is taken as marginal. A case where thepolymer was not dissolved therein is taken as poor. The results areshown in Table 1.

(Manufacture of Thin Film)

The above-described polymer was dissolved in NMP to be 2.5% by weight,and filtrated with a filter having a pore size of 0.2 μm to obtain anapplication liquid. The application liquid obtained was spin-coated on asynthetic quartz substrate having a size of 2 cm×2 cm and a thickness of1 mm at 2000 rpm for 60 seconds, and uniformly coated thereon.

Then, the resulting material was heated and dried on a hot plate at 200°C. for 30 minutes to evaporate the solvent to form a thin film of thepolymer thereon.

(Optical Evaluation)

The thin film obtained was measured using a spectroscopic ellipsometerM-2000D (made by J.A. Woollam Company, attached with NIR option), andanalyzed by a general dispersion formulation model to determine arefractive index n and an extinction coefficient k in the wavelengthrange of 190 to 1700 nm. Then, no, the Abbe number and k₄₀₀ determinedare shown in Table 1.

In addition, the Abbe number means a numerical value representingwavelength dispersion of the refractive index, and was calculatedaccording to an equation: (n_(D)−1)/(n_(F)−n_(C)). Then, n_(D), n_(F)and n_(C) are as described below:

n_(D): a refractive index of a D line (589.3 nm);

n_(F): a refractive index of an F line (486.1 nm); and

n_(C): a refractive index of a C line (656.3 nm).

Then, k₄₀₀ represents the extinction coefficient k in light having awavelength of 400 nm, and represents that, as k₄₀₀ is smaller,transparency in a visible light wavelength region is higher, andvisually observed coloration is weaker.

Examples 2 to 13 and Comparative Example 1

In Examples 2 to 9, Examples 11 to 13 and Comparative Example 1, apolymer was manufactured and evaluated in the same manner as in Example1 except that a diamine monomer, a dichloro monomer, a polymerizationsolvent, a polymerization atmosphere and a polymerization temperatureshown in Tables 1 and 2 were used. The results are shown in Tables 1 and2.

In Example 10, a polymer was manufactured and evaluated in the samemanner as in Example 1 except that a dichloro monomer was put in a 100mL three-necked flask in place of the diamine monomer and a diaminemonomer was used in place of the dichloro monomer to be chargedthereinto with the syringe. The results are shown in Tables 1 or 2.

In Table 1, both super dehydrated DMA and super dehydrated DMF are madeby Wako Pure Chemical Industries, Ltd.

In Table 2, all of super dehydrated NMP, guaranteed DMA and superdehydrated DMA are made by Wako Pure Chemical Industries, Ltd.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Diamine monomerp-Phenylenediamine p-Phenylenediamine p-Phenylenediaminep-Phenylenediamine Dichloro monomer A-1 A-1 A-1 A-1 Polymerizationsolvent Super dehydrated Super dehydrated Super dehydrated Superdehydrated DMA DMA DMA DMA Polymerization atmosphere Nitrogen NitrogenNitrogen Nitrogen Polymerization temperature (° C.) 150 130 120 100 Mp2593 2651 4453 5482 Powder color White Pale yellow Pale yellow YellowSolubility in isophorone 1 Good Good Good Marginal Solubility inisophorone 2 Marginal Marginal Marginal Marginal Solubility in PGME 1Good Good Marginal Marginal Solubility in PGME 2 Marginal MarginalMarginal Marginal Solubility in DMA 1 Good Good Good Good Solubility inDMA 2 Good Good Good Good Solubility in DMF 1 Good Good Good GoodSolubility in DMF 2 Good Good Good Good Solubility in NMP 1 Good GoodGood Good Solubility in NMP 2 Good Good Good Good Solubility in GoodGood Good Good 1,3-dimethyl-2-imidazolidinone 1 Solubility in Good GoodGood Good 1,3-dimethyl-2-imidazolidinone 2 n_(D) 1.9918 1.9324 1.95471.9814 Abbe number 11.17 11.95 11.45 11.23 k₄₀₀ 1.95 × 10⁻³ 3.45 × 10⁻³3.75 × 10⁻³ 2.58 × 10⁻² Example 5 Example 6 Example 7 Diamine monomerp-Phenylenediamine p-Phenylenediamine p-Phenylenediamine Dichloromonomer A-1 A-1 A-1 Polymerization solvent Super dehydrated DMA Superdehydrated DMA Super dehydrated DMF Polymerization atmosphere NitrogenNitrogen Nitrogen Polymerization temperature (° C.) 80 60 150 Mp 59978328 5205 Powder color Yellow Orange Yellow Solubility in isophorone 1Marginal Marginal Marginal Solubility in isophorone 2 Marginal MarginalMarginal Solubility in PGME 1 Marginal Marginal Marginal Solubility inPGME 2 Marginal Marginal Marginal Solubility in DMA 1 Good Good GoodSolubility in DMA 2 Good Good Good Solubility in DMF 1 Good Good GoodSolubility in DMF 2 Good Good Good Solubility in NMP 1 Good Good GoodSolubility in NMP 2 Good Good Good Solubility in Good Good Good1,3-dimethyl-2-imidazolidinone 1 Solubility in Good Good Good1,3-dimethyl-2-imidazolidinone 2 n_(D) 1.9681 1.9482 1.9324 Abbe number11.37 11.84 11.82 k₄₀₀ 5.56 × 10⁻² 9.35 × 10⁻² 3.24 × 10⁻²

TABLE 2 Example 8 Example 9 Example 10 Example 11 Diamine monomerp-Phenylenediamine p-Phenylenediamine p-Phenylenediaminem-Phenylenediamine Dichloro monomer A-1 A-1 A-1 A-1 Polymerizationsolvent Super dehydrated NMP Guaranteed DMA Super dehydrated DMA Superdehydrated DMA Polymerization atmosphere Nitrogen Air Nitrogen NitrogenPolymerization temperature (° C.) 100 120 150 150 Mp 6258 4312 1529 3744Powder color Orange Deep orange Yellow White 10% by weight in isophoroneMarginal Marginal Marginal Good 20% by weight in isophorone MarginalMarginal Marginal Marginal 10% by weight in PGME Marginal MarginalMarginal Marginal 20% by weight in PGME Marginal Marginal MarginalMarginal Solubility in DMA 1 Good Good Good Good Solubility in DMA 2Good Good Good Good Solubility in DMF 1 Good Good Good Good Solubilityin DMF 2 Good Good Good Good Solubility in NMP 1 Good Good Good GoodSolubility in NMP 2 Good Good Good Good Solubility in Good Good GoodGood 1,3-dimethyl-2-imidazolidinone 1 Solubility in Good Good Good Good1,3-dimethyl-2-imidazolidinone 2 n_(D) 1.9526 1.9617 1.9645 1.9272 Abbenumber 11.87 11.51 11.49 12.56 k₄₀₀ 8.41 × 10² 2.91 × 10⁻¹ 5.74 × 10⁻²2.08 × 10⁻³ Example 12 Example 13 Comp. Ex. 1 Diamine monomerm-Phenylenediamine m-Phenylenediamine p-Phenylenediamine Dichloromonomer A-1 A-1 A-1 Polymerization solvent Super dehydrated DMAGuaranteed DMA Super dehydrated NMP Polymerization atmosphere NitrogenNitrogen Nitrogen Polymerization temperature (° C.) 120 120 150 Mp 38543657 19632 Powder color Pale yellow Yellow Yellow 10% by weight inisophorone Good Good Poor 20% by weight in isophorone Marginal MarginalPoor 10% by weight in PGME Marginal Marginal Poor 20% by weight in PGMEMarginal Marginal Poor Solubility in DMA 1 Good Good Good Solubility inDMA 2 Good Good Good Solubility in DMF 1 Good Good Good Solubility inDMF 2 Good Good Good Solubility in NMP 1 Good Good Good Solubility inNMP 2 Good Good Good Solubility in Good Good Good1,3-dimethyl-2-imidazolidinone 1 Solubility in Good Good Good1,3-dimethyl-2-imidazolidinone 2 n_(D) 1.9358 1.9189 1.9274 Abbe number12.34 12.68 11.94 k₄₀₀ 4.25 × 10⁻³ 1.76 × 10⁻² 1.54 × 10⁻²

Examples 14 to 19

A polymer was manufactured and evaluated in the same manner as inExample 1 except that an end-capping agent shown in Table 3 was used inplace of 4-isopropylaniline. The results are shown in Table 3.

TABLE 3 Example 14 Example 15 Example 16 Example 17 Example 18 Example19 End-capping agent Aniline n- 3-(Trimethoxysilyl)-3-[3′-(Trimethoxysilyl)- Hexamethyldisilazane None Butylaminepropylamine aminopropyl]- aminopropylamine Mp 2527 2538 2603 2635 25812501 Powder color Pale yellow Pale yellow Pale yellow Pale yellow Paleyellow Yellow 10% by weight in isophorone Good Good Good Good GoodMarginal 20% by weight in isophorone Marginal Good Good Good GoodMarginal 10% by weight in PGME Good Good Good Good Good Marginal 20% byweight in PGME Marginal Marginal Good Good Marginal Marginal Solubilityin DMA 1 Good Good Good Good Good Good Solubility in DMA 2 Good GoodGood Good Good Good Solubility in DMF 1 Good Good Good Good Good GoodSolubility in DMF 2 Good Good Good Good Good Good Solubility in NMP 1Good Good Good Good Good Good Solubility in NMP 2 Good Good Good GoodGood Good Solubility in Good Good Good Good Good Good1,3-dimethyl-2-imidazolidinone 1 Solubility in Good Good Good Good GoodGood 1,3-dimethyl-2-imidazolidinone 2 n_(D) 1.9313 1.9225 1.91 1.88951.9352 1.9147 Abbe number 11.21 10.97 11.18 11.55 11.1 11.25 k₄₀₀ 3.10 ×10⁻³ 6.04 × 10⁻³ 4.84 × 10⁻³ 2.40 × 10⁻³ 5.17 × 10⁻³ 1.42 × 10⁻²

Example 20

A polymer (mixture of a polymer represented by the following formula(B-2) and a polymer represented by the following formula (B-2′)(wherein, each formula indicates that a structural unit in brackets isrepeated.)) was obtained by manufacturing the polymer in the same manneras in Example 1 except that the compound A-2 obtained in SynthesisExample 2 was used as a dichloro monomer in place of the compound A-1.The polymer obtained was evaluated in the same manner as in Example 1.The results are shown in Table 4.

Example 21

A polymer (mixture of a polymer represented by the following formula(B-3) and a polymer represented by the following formula (B-3′)(wherein, each formula indicates that a structural unit in brackets isrepeated.)) was obtained by manufacturing the polymer in the same manneras in Example 1 except that the compound A-3 obtained in SynthesisExample 3 was used as a dichloro monomer in place of the compound A-1.The polymer obtained was evaluated in the same manner as in Example 1.The results are shown in Table 4.

TABLE 4 Example 20 Example 21 Diamine monomer p-Phenylenediaminep-Phenylenediamine Dichloro monomer A-2 A-3 Mp 2456 2548 Powder colorDeep orange White 10% by weight in isophorone Good Good 20% by weight inisophorone Marginal Marginal 10% by weight in PGME Good Good 20% byweight in PGME Marginal Marginal Solubility in DMA 1 Good GoodSolubility in DMA 2 Good Good Solubility in DMF 1 Good Good Solubilityin DMF 2 Good Good Solubility in NMP 1 Good Good Solubility in NMP 2Good Good Solubility in Good Good 1,3-dimethyl-2- imidazolidinone 1Solubility in Good Good 1,3-dimethyl-2- imidazolidinone 2 n_(D) 1.99661.7406 Abbe number 7.03 14.08 k₄₀₀ 3.18 × 10⁻¹ 1.99 × 10⁻³

INDUSTRIAL APPLICABILITY

A triazine ring-containing polymer and a composition according to theinvention can be used for a thin film, a film, a transparent plate, alens or the like, and the thin film, the film, the transparent plate orthe lens according to the invention can be used for an electronicdevice, a light-emitting device, an optical device or the like.

Several embodiments and/or Examples of the invention have been describedin detail above, but those skilled in the art will readily make a greatnumber of modifications to the exemplary embodiments and/or Exampleswithout substantially departing from new teachings and advantageouseffects of the invention. Accordingly, all such modifications areincluded within the scope of the invention.

The entire contents of the description of the Japanese applicationserving as a basis of claiming the priority concerning the presentapplication to the Paris Convention are incorporated by referenceherein.

1: A triazine ring-containing polymer, comprising a structural unitrepresented by the following formula (1), wherein a peak top molecularweight obtained by gel permeation chromatography is 19,000 or less:

wherein, A represents a divalent group selected from the groupconsisting of —NH—, —NR″—, —NH—(C═O)—, —NR″—(C═O)—, —S— and —O—; R′represents a divalent aliphatic hydrocarbon group, a divalent aromatichydrocarbon group, or a divalent group which is a combination of (i) oneor more selected from the group consisting of one or more divalentaliphatic hydrocarbon groups and one or more divalent aromatichydrocarbon groups, and (ii) one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—; and R′ may be furthersubstituted with a substituent; R represents a hydrogen atom, analiphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatichydrocarbon group comprising a group which is a combination of anaromatic hydrocarbon group and one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O— and —(C═O)—, an aromatic hydrocarbongroup comprising a group which is a combination of an aliphatichydrocarbon group and one or more selected from the group consisting ofa single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—,—(C═O)—O— and —(C═O)—, or an acetyl group; and R may be furthersubstituted with a substituent; and R″ represents an aliphatichydrocarbon group, an aromatic hydrocarbon group, or a group which is acombination of one or more aliphatic hydrocarbon groups and one or morearomatic hydrocarbon groups; and when a plurality of R″ exist, theplurality of R″ may be the same with or different from each other. 2:The triazine ring-containing polymer of claim 1, wherein an end groupcomprises an amino group, —NHR¹ or —N(R¹)₂, wherein R¹ independentlyrepresents —Si(R″)₃, —Si(OR″)₃, a group which is a combination of—Si(OR″)₃ and a divalent group, R^(a)—(C═O)—, an aliphatic hydrocarbongroup, an aromatic hydrocarbon group, an aliphatic hydrocarbon groupcomprising a group which is a combination of an aromatic hydrocarbongroup and one or more selected from the group consisting of a singlebond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—, —(C═O)—NH—, —O—(C═O)—O—,—(C═O)—O—, —(C═O)—, a silylene group and a siloxylene group, or anaromatic hydrocarbon group comprising a group which is a combination ofan aliphatic hydrocarbon group and one or more selected from the groupconsisting of a single bond, —S—, —S(═O)₂—, —O—, —NH—, —NR″—,—(C═O)—NH—, —O—(C═O)—O—, —(C═O)—O—, —(C═O)—, a silylene group and asiloxylene group; and R¹ may be further substituted with a substituent;R^(a) represents an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, or an aliphatic hydrocarbon group comprising an aromatichydrocarbon group; and R″ represents an aliphatic hydrocarbon group, anaromatic hydrocarbon group, or a group which is a combination of one ormore aliphatic hydrocarbon groups and one or more aromatic hydrocarbongroups. 3: The triazine ring-containing polymer of claim 1, wherein anextinction coefficient at a wavelength of 400 nm is 0.01 or less. 4: Thetriazine ring-containing polymer of claim 1, wherein R is an aliphatichydrocarbon group which may comprise a substituent or an aromatichydrocarbon group which may comprise a substituent, and R′ is a divalentgroup represented by any of the following formulas (5) to (11):

5: The triazine ring-containing polymer of claim 1, wherein R is aphenyl group, a p-cyanophenyl group or a p-nitrophenyl group. 6: Acomposition, comprising the triazine ring-containing polymer of claim 1,and an organic solvent. 7: The composition of claim 6, furthercomprising one or more selected from the group consisting of an organicpolymer, an inorganic polymer and an organic-inorganic hybrid polymer.8: The composition of claim 6, further comprising an ultraviolet curingagent or a thermosetting agent. 9: A thin film, a film, a transparentplate or a lens, prepared by using the triazine ring-containing polymeraccording to claim
 1. 10: An electronic device, a light-emitting deviceor an optical device, comprising the thin film, the film, thetransparent plate or the lens of claim
 9. 11: A thin film, a film, atransparent plate or a lens, prepared by using the composition of claim6. 12: An electronic device, a light-emitting device or an opticaldevice, comprising the thin film, the film, the transparent plate or thelens of claim 11.